Cesium carbonate → HCID 68109336, compound

HRID 2179425Notes

Reaction equation

HRID 2179425 reaction equation
Br[C:2]1[C:7]2[O:8][C:9]3[NH:14][CH:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12][CH:11]([CH3:22])[C:10]=3[C:6]=2[CH:5]=[C:4]([Cl:23])[CH:3]=1.[C:24]1([S:30]([O-:32])=[O:31])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[Na+].C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1(C)C=CC=CC=1>[Cl:23][C:4]1[CH:3]=[C:2]([S:30]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)(=[O:32])=[O:31])[C:7]2[O:8][C:9]3[NH:14][CH:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:12][CH:11]([CH3:22])[C:10]=3[C:6]=2[CH:5]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2723840Benzenesulfinic acid, sodium saltHCID 68109726HCID 68109726, compound

Product 1

HCID 68109336HCID 68109336, compoundYield 29.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of the product of step B (560 mg, 1.39 mmol), sodium benzenesulfinate (275 mg, 1.67 mmol), di-palladium-tris(dibenzylideneacetone) (179 mg, 0.19 mmol), cesium carbonate (683 mg, 2.09 mmol) and xantphos (225 mg, 0.39 mmol) were suspended in anhydrous toluene (20 mL). The reaction flask was purged with argon and heated to 110° C. for 6 h. After cooling to ambient temperature, the reaction was diluted with dichloromethane and filtered through a celite bed. The filtrate was concentrated in vacuo and the residue purified by flash column chromatography (SiO2, 4:1 hexanes/ethyl acetate) to give tert-butyl 6-chloro-4-methyl-8-(phenylsulfonyl)-3,4-dihydrobenzofuro[3,2-e]pyridine-2(1H)-carboxylate (190 mg, 29%) as an off-white solid: 1H NMR (CDCl3, 300 MHz) δ 8.01-7.93 (m, 3H), 7.84 (s, 1H), 7.61-7.47 (m, 3H), 4.63-4.47 (m, 2H), 4.08-3.75 (m, 1H), 3.58-3.27 (m, 1H), 3.21-3.08 (m, 1H), 1.51 (s, 9H), 1.33 (d, J=6.9 Hz, 3H).

Workup

  1. customThe reaction flask was purged with argon
  2. temperatureAfter cooling to ambient temperature
  3. additionthe reaction was diluted with dichloromethane
  4. filtrationfiltered through a celite bed
  5. concentrationThe filtrate was concentrated in vacuo
  6. customthe residue purified by flash column chromatography (SiO2, 4:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-1d0691d6c5334ea285ebdf6e51d5358f
Source dataset
uspto-grants-2015_06
Patent number
US09067949B2

Reaction notes

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